Partially fluorinated sulfonated surfactants

ABSTRACT

The present invention comprises a compound comprising Formula 1A, 1B, or 1C 
       (R a —O—CO—) 2 X  Formula 1A 
       R a —O—CO—X—CO—O—(CH 2 CH 2 )R f   Formula 1B 
       R a —O—CO—X—CO—O—R  Formula 1C 
     wherein
         R a  is the group R f (CH 2 CF 2 ) d —(C g H 2g )—; R f OCF 2 CF 2 —(C g H 2g )—; R f OCFHCF 2 O(CH 2 CH 2 O) v —(C g H 2g )—; R f OCFHCF 2 O(C w H 2w ); R f OCF(CF 3 )CONH—(C g H 2g ); or R f (CH 2 ) h [(CF 2 CF 2 ) i (CH 2 CH 2 ) j ] k ;   R f  is C c F (2c+1) ;   d is 1 to about 3; g is 1 to 4; v is 1 to about 4; w is from about 3 to about 12; h is 1 to about 6; i, j, and k are each independently 1, 2, or 3, or a mixture thereof; provided that the total number of carbon atoms in group (vi) is from about 8 to about 22;   X is a linear or branched difunctional alkyl sulfonate group —C e H (2e−1) (SO 3 M)-, wherein e is 2 or 3;   M is a monovalent cation selected from the group consisting of hydrogen, ammonium, alkali metal, or alkaline earth metal;   R is H or a linear or branched alkyl group C b H (2b+1) —; and   b is from 1 to about 18.

BACKGROUND OF THE INVENTION

Historically, many fluoroalkyl surfactants were based on theperfluoroalkylethanols, F(CF₂CF₂)_(q)CH₂CH₂OH, the so-called “Telomer Balcohols”, where q was typically about 2 to 10. The Telomer B alcoholsand their preparation are described by Kirchner et al. in U.S. Pat. No.5,202,506. Other fluoroalkyl surfactants based on Telomer B alcoholshave included “twin-tailed” anionic surfactants such asF(CF₂CF₂)_(q)(CH₂CH₂)OCOCH₂CH(SO₃Na)COO(CH₂CH₂)(CF₂CF₂)_(q)F, where q isas defined above, prepared by firstly reacting two moles of one or moreperfluoroalkylethanols with one of maleic anhydride and, secondly,reacting the diester product with sodium hydrogen sulfite solution, asdescribed, for instance, by Yoshino et al. in “Surfactants havingpolyfluoroalkyl chains. II. Syntheses of anionic surfactants having twopolyfluoroalkyl chains including a trifluoromethyl group at each tailand their flocculation-redispersion ability for dispersed magnetiteparticles in water”, Journal of Fluorine Chemistry (1995), 70(2),187-91. Yoshino et al. reported examples wherein q was 2, 3, and 4 foruse in supercritical carbon dioxide. Yoshino et al. report twin-tailedsurfactants wherein both end groups are limited to perfluoroalkylgroups.

Nagai et al. in US Patent Application 2008/0093582, describe twin-tailedsurfactants of the structure

R_(f)—(CH₂)_(n1)—(X¹)_(p1)—CH(SO₃M)(X²)_(q1)—R_(h)

wherein R_(f) is a fluoroalkyl group that may contain an ether bond, X¹and X² are the same or different divalent linking groups; M is H, analkali metal, half an alkaline earth metal, or ammonium; R_(h) is analkyl group; n1 is an integer of 1 to 10; and p1 and q1 are each 0 or 1.

One common route to perfluoroalkylethanols used to make such surfactantsis a multi-step process using tetrafluoroethylene. Tetrafluoroethyleneis a hazardous and expensive intermediate with limited availability. Itis desirable to provide fluorinated surfactants that use less or notetrafluoroethylene in their preparation.

It is also desirable to provide new and improved fluorinated surfactantsin which the perfluoroalkyl group of the prior art is replaced bypartially fluorinated terminal groups that require lesstetrafluoroethylene and show increased fluorine efficiency. By “fluorineefficiency” is meant the ability to use a minimum amount offluorochemical to obtain a desired surface effect or surfactantproperties, when applied to substrates, or to obtain better performanceusing the same level of fluorine. A polymer having high fluorineefficiency generates the same or greater level of surface effect using alower amount of fluorine than a comparative polymer. The presentinvention provides such improved fluorinated surfactants.

SUMMARY OF THE INVENTION

The present invention comprises a compound comprising Formula 1A, 1B, or1C

(R_(a)—O—CO—)₂X  Formula 1A

R_(a)—O—CO—X—CO—O—(CH₂CH₂)R_(f)  Formula 1B

R_(a)—O—CO—X—CO—O—R  Formula 1C

wherein

R_(a) is the group

(i) R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—;

(ii) R_(f)OCF₂CF₂—(C_(g)H_(2g))—;

(iii) R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—;

(iv) R_(f)OCFHCF₂O(C_(w)H_(2w))—; (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g))—;or

(vi) R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)—

-   -   each R_(f) is independently C_(c)F_((2c+1));    -   c is 2 to about 6;    -   d is 1 to about 3;    -   g is 1 to about 4;    -   v is 1 to about 4;    -   w is from about 3 to about 12;    -   h is 1 to about 6;    -   i, j, and k are each independently 1, 2, or 3, or a mixture        thereof; provided that the total number of carbon atoms in        group (vi) is from about 8 to about 22;    -   X is a linear or branched difunctional alkyl sulfonate group

—C_(e)H_((2e−1))(SO₃M)-,

wherein

e is 2 or 3.

M is a monovalent cation selected from the group consisting of hydrogen,ammonium, alkali metal, and alkaline earth metal;

R is H or a linear or branched alkyl group C_(b)H_((2b+1))—; and

b is from 1 to about 18.

The present invention further comprises a method of altering the surfacebehavior of a liquid comprising adding to the liquid a compound ofFormula 1A, 1B or 1C as described above, or a mixture thereof.

DETAILED DESCRIPTION

Herein trademarks are shown in upper case.

The surfactants of the present invention have the structure of Formulae1A, 1B, or 1C.

(R_(a)—O—CO—)₂X  Formula 1A

R_(a)—O—CO—X—CO—O—(CH₂CH₂)R_(f)  Formula 1B

R_(a)—O—CO—X—CO—O—R  Formula 1C

wherein

R is H or a linear or branched alkyl group C_(b)H_((2b+1))— wherein b isfrom 1 to about 18, preferably from about 6 to about 18;

each R_(f) is independently C_(c)F_((2c+1)) having c of from about 2 toabout 6, preferably from 2 to 4, and more preferably 4;

X is a linear or branched difunctional alkyl sulfonate group

—C_(e)H_((2e−1))(SO₃M)-,

wherein e is from 2 or 3, preferably 3; and M is a monovalent cationwhich is hydrogen, ammonium, alkali metal, or alkaline earth metal, andis preferably Na;

R_(a) is selected from the group consisting of structure (i) through(vi) wherein R_(f) is as defined above, and g is 1 to about 4,preferably from 1 to 3, and more preferably 2:

-   -   (i) R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))— wherein d is 1 to about 3,        preferably from 1 to 2, and more preferably 1;    -   (ii) R_(f)OCF₂CF₂—(C_(g)H_(2g))—;    -   (iii) R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))— wherein v is 1        to about 4, preferably from 1 to 2, and more preferably 2;    -   (iv) R_(f)OCFHCF₂O(C_(w)H_(2w))— wherein w is from about 3 to        about 12, preferably from 4 to 6, and more preferably 4;    -   (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g))—; or    -   (vi) R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k) wherein h is 1        to about 6, preferably from 1 to 3, and more preferably 1; and        i, j, and k are each independently 1, 2, or 3, or a mixture        thereof, preferably 1 or 2, and more preferably 1; provided that        the total number of carbon atoms in group (vi) is from about 8        to about 22. The preferred R_(a) groups are (i), (ii), (iii),        and (iv).

Preferred embodiments of Formula 1A, 1B and 1C are those wherein Ra isgroup (i) R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—, (ii)R_(f)OCF₂CF₂—(C_(g)H_(2g))—; (iii)R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—; or (iv)R_(f)OCFHCF₂O(C_(w)H_(2w))—; when c is 3 or 4; and X is CH₂CH(SO₃M),CH₂CH(CH₂SO₃M), CH(CH₃)CH(SO₃M), CH₂CH(SO₃M)CH₂, or CH₂CH(SO₃M)CH₂CH₂.More specifically preferred embodiments of Formula 1A, 1B and 1C arewhen d is 1, g is 1 or 2, and R_(f) is C₃F₇ or C₄F₉. Also specificallypreferred are compounds wherein R_(f) is C₃F₇ or C₄F₉ and X isC₃H₅(SO₃Na) or CH₂CH(SO₃Na). The compound of Formula 1B wherein R_(a) isC₄F₉CH₂CF₂CH₂CH₂ or C₃F₇CH₂CF₂CH₂CH₂ and R_(f) is (CF₂)₆F is alsopreferred.

A preferred embodiment of Formula 1A (R_(a)OCO—X—COOR_(a)) isC₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)OCH₂CH₂CF₂CH₂C₄F₉.

A preferred embodiment of Formula 1B isC₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)OCH₂CH₂(CF₂)₆F.

A preferred embodiment of Formula 1C isC₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O(CH₂)₆H.

The surfactants of Formulae 1A, 1B, and 1C economize on the use oftetrafluoroethylene in their preparation and provide comparable orimproved surfactant properties, versus prior art surfactants derivedfrom Telomer B alcohols.

The surfactants of Formulae 1A, 1B, and 1C are prepared via theunsaturated intermediates of Formulae 2A, 2B, and 2C according to thefollowing Reaction Scheme A:

The unsaturated intermediates used in the preparation of Formula 1A, 1Band 1C are compounds of Formula 2A, 2B and 2C:

(R_(a)—O—CO—)₂Y  Formula 2A

R_(a)—O—CO—Y—CO—O—(CH₂CH₂)R_(f)  Formula 2B

R_(a)—O—CO—Y—CO—O—R  Formula 2C

wherein

R_(a) is the group

-   (i) R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—;-   (ii) R_(f)OCF₂CF₂—(C_(g)H_(2g))—;-   (iii) R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—;-   (iv) R_(f)OCFHCF₂O(C_(w)H_(2w))—;-   (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g))—; or-   (vi) R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)—

each R_(f) is independently C_(c)F_((2c+1));

c is 2 to about 6, preferably from 2 to 4, more preferably 4;

d is 1 to about 3, preferably from 1 to 2, more preferably 1;

g is 1 to 4, preferably from 1 to 3, more preferably 2;

v is 1 to about 4, preferably from 2 to 3, more preferably 2;

w is from about 3 to about 12, preferably from 4 to 6, more preferably4;

h is 1 to about 6, preferably from 1 to 3, more preferably 2;

i, j, and k are each independently 1, 2, or 3, or a mixture thereof,preferably 1 or 2, more preferably 1;

provided that the total number of carbon atoms in group (vi) is fromabout 8 to about 22;

Y is a linear or branched diradical having olefinic unsaturation of theformula

—C_(e)H_((2e−2))—

wherein

e is 2 or 3, preferably 2;

R is H or a linear or branched alkyl group C_(b)H_((2b+1))—; and

b is from 1 to about 18, preferably from 6 to 18.

The surfactants of Formula 1A are prepared by reacting two moles offluoroalcohols of formula R_(a)—OH wherein R_(a) is defined as abovewith one mole of an unsaturated linear or branched dibasic acid of thestructure C_(e)H_((2e−2))(COOH)₂ or its anhydride of Formula D

wherein e is 2 or 3 to form the unsaturated diester of Formula 2A as anintermediate. Methods for carboxylic acid esterification areconventional as discussed by Jain and Masse in “Carboxylic acid esters:synthesis from carboxylic acids and derivatives” in Science of Synthesis(2006), 20b, 711-723. An acid catalyst or dehydrating agent is preferredwhen reacting the free acid groups with alcohols. An example of an acidcatalyst is p-toluenesulfonic acid in toluene, and an example of adehydrating agent is dicyclohexylcarbodiimide in methylene chloride.Preferred unsaturated dibasic acids and corresponding anhydrides aremaleic, itaconic (methylenesuccinic acid), citraconic (methylmaleicacid), trans-glutaconic (HOOCCH₂CH═CHCOOH), and trans-beta-hydromuconic(HOOCCH₂CH═CHCH₂COOH) acids and anhydrides. The unsaturated diester ofFormula 2A is then reacted with aqueous sodium hydrogen sulfite to formthe sulfonic acid. Sulfonation techniques are described by Roberts in“Sulfonation Technology for Anionic Surfactant Manufacture”, OrganicProcess Research & Development 1998, 2, 194-202, and by Sekiguchi et al.in U.S. Pat. No. 4,545,939. Alternatively, the olefinic precursorsdescribed above can be converted to the sulfonates of Formulae 1A, 1B,and 1C by the addition of sulfur trioxide to the double bond. The freesulfonic acid can be used as the surfactant, or the sulfonic acid can beconverted to the ammonium salt, the alkali metal salt, or an alkalineearth metal salt, and preferably to the sodium salt. Those skilled inthe art will recognize other sulfonation methods, such as thosedescribed by Roberts and Sekiguchi (above) are applicable and areincluded in the present invention.

Addition of the sulfonate group across the double bond of Formulae 1A,1B, and 1C to make the surfactants of Formulae 2A, 2B, and 2C results inthe formation of stereo-isomers and regio-isomers. For the purposes ofthe present invention, all the isomers are equivalent and all areincluded in the definitions of Formulae 2A, 2B, and 2C.

The surfactants of Formulae 1B and 1C are prepared by reacting one moleof a fluoroalcohol of formula R_(a)—OH with one mole of an unsaturatedlinear or branched dibasic acid anhydride of the structure of Formula Dat a lower temperature (between about 50-85° C.). The esterification isthen continued at a higher temperature (between about 100-120° C.) witha mole of a fluoroalcohol, preferably of formula R_(f)CH₂CH₂—OH, toproduce Formula 2B, or a mole of alcohol of formula R—OH, to produceFormula 2C. Any of a variety of conventional fluorinated alcohols aresuitable for use at this point of the process. This is followed byconversion to the sulfonates. The anhydride is preferred in thepreparation of surfactants of Formulae 1B and 1C. The opening of theanhydride ring by the first esterification is a faster reaction than thesecond esterification of the intermediate acid ester. As indicatedabove, in the second esterification acid catalysts or dehydrating agentsare used. Use of the dibasic acid thus tends to give mixtures ofproducts. The sequence of use of the two alcohols in the esterificationscan be reversed.

The surfactants of Formula 1A can also be prepared using two additionsof the same alcohol and the two-temperature procedure described forFormulae 1B and 1C, followed by conversion to the sulfonates. However,this two-step procedure is not preferred.

Mixtures of surfactants of compositions of Formulae 1A, 1B, and 1C canbe prepared by using two moles of a mixture of two or more of R_(a)—OH,R_(f)—CH₂CH₂—OH, and R—OH alcohols. The two moles of a mixture of two ormore alcohols are reacted with one mole of an unsaturated linear orbranched dibasic acid of the structure C_(e)H_((2e−2))(COOH)₂ or itsanhydride (Formula D) as described above for the preparation ofsurfactants of Formula 1A, followed by conversion to the sulfonates.Such surfactant mixtures can be used as is or separated into thecomponent fractions. Such separations are not preferred.

Alcohols containing the R_(a) group (i) of R_(f)(CH₂CF₂)_(d)—CH₂CH₂—useful in the invention include the fluorinated telomer alcohols offormula (V):

R_(f)—(CH₂CF₂)_(q)(CH₂CH₂)_(r)—OH  (V)

wherein R_(f) is a linear or branched perfluoroalkyl group having 2 to 6carbon atoms, and subscripts q and r are each independently integers of1 to 3. These telomer alcohols are available by synthesis according toScheme 1 wherein R_(f), q and r are as defined for Formula (V).

The telomerization of vinylidene fluoride with linear or branchedperfluoroalkyl iodides produces compounds of the structure R_(f)(CH₂CF₂)_(q)I, wherein, q is 1 or more and R_(f) is a C₂ to C₆perfluoroalkyl group. For example, see Balague, et al, “Synthesis offluorinated telomers, Part 1, Telomerization of vinylidene fluoride withperfluoroalkyl iodides”, J. Fluorine Chem. (1995), 70(2), 215-23. Thespecific telomer iodides are isolated by fractional distillation. Thetelomer iodides are treated with ethylene by procedures described inU.S. Pat. No. 3,979,469 to provide the telomer ethylene iodides (VI ofScheme 1) wherein r is 1 to 3 or more. The telomer ethylene iodides (VIof Scheme 1) are treated with oleum and hydrolyzed to provide thecorresponding telomer alcohols (V of Scheme 1) according to proceduresdisclosed in WO 95/11877. Alternatively, the telomer ethylene iodides(VI of Scheme 1) can be treated with N-methyl formamide followed byethyl alcohol/acid hydrolysis.

The R_(a) group of Formula (ii) R_(f)OCF₂CF₂(C_(g)H_(2g))—, is obtainedby preparing fluoroalcohols of the formula R_(f)OCF₂CF₂—CH₂CH₂OH whichare available by the following series of reactions wherein R_(f) is alinear or branched C₂ to C₆ perfluoroalkyl optionally interrupted by oneto three oxygen atoms and q is an integer of 1 to 3:

The perfluoroalkyl ether iodides of formula (V of Scheme 2) above can bemade by the procedure described in U.S. Pat. No. 5,481,028, hereinincorporated by reference, in Example 8, which discloses the preparationof compounds of formula (V of Scheme 2) from perfluoro-n-propyl vinylether. The perfluoalkyl ether iodide (V of Scheme 2) is reacted with anexcess of ethylene at an elevated temperature and pressure. While theaddition of ethylene can be carried out thermally, the use of a suitablecatalyst is preferred. Preferably the catalyst is a peroxide catalystsuch as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, oracetyl peroxide. More preferably the peroxide catalyst is benzoylperoxide. The temperature of the reaction is not limited, but atemperature in the range of 110° C. to 130° C. is preferred. Thereaction time can vary with the catalyst and reaction conditions, but 24hours is usually adequate. The product is purified by any means thatseparates unreacted starting material from the final product, butdistillation is preferred. Satisfactory yields up to 80% of theory havebeen obtained using about 2.7 mols of ethylene per mole of perfluoalkylether iodide, a temperature of 110° C. and autogenous pressure, areaction time of 24 hours, and purifying the product by distillation.

The perfluoroalkylether ethylene iodides (VI of Scheme 2) are treatedwith oleum and hydrolyzed to provide the corresponding alcohols (VII ofScheme 2) according to procedures disclosed in WO 95/11877 (Elf AtochemS.A.). Alternatively, the perfluoroalkylether ethyl iodides can betreated with N-methyl formamide followed by ethyl alcohol/acidhydrolysis. A temperature of about 130° to 160° C. is preferred.

The R_(a) group of Formula (iii),R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—, is prepared by reacting afluorinated vinyl ether with a polyethylene glycol. Typically the vinylether is slowly added to the glycol in a molar ratio of from about 1:1to about 3:1, preferably at about 2:1. The reaction is conducted in thepresence of sodium hydride, which is a catalyst that is basic enough togenerate equilibrium amounts of the alkoxide anion from the glycol.Other suitable base catalysts include potassium hydride, sodium amide,lithium amide, potassium tert-butoxide, and potassium hydroxide. Thereaction is conducted under an inert atmosphere such as nitrogen gas.Suitable solvents include dimethylformamide, dimethylacetamide,acetonitrile, tetrahydrofuran, and dioxane. Preferred isdimethylformamide. Cooling is employed to maintain the reactiontemperature at from about 0° C. to about 30° C. The reaction is usuallyconducted for 1 to about 18 hours. The solvent is then removed usingconventional techniques; such as evaporation in vacuum on a rotaryevaporator, or in cases where the product is water insoluble and thesolvent is water soluble, addition of the mixture to an excess of waterfollowed by separation of the layers.

The reaction of perfluoropropyl vinyl ether with polyethylene glycoldoes not always go to completion. The average degree of conversion ofthe polyethylene glycol hydroxyl groups can be determined by ¹H NMRspectroscopy. Typically mixtures of unreacted polyethylene glycol, theproduct of fluorinated vinyl ether adding to one end of polyethyleneglycol (for example, structure B below), and the product of fluorinatedvinyl ether adding to both ends of the polyethylene glycol (for example,structure A below) can be obtained. The relative amounts of thecomponents of the mixture are affected by the ratio of the reactants,the reaction conditions, and the way in which the product is isolated.High ratios of the vinyl ether to glycol and long reaction times tend tofavor Structure A, shown below. Lower ratios of vinyl ether to glycoland shorter reaction times give increased amounts of Structure B, shownbelow, and unreacted polyethylene glycol. It is sometimes possible touse the differences in solubility between Structures A, B, and thestarting glycol to do selective solvent extraction of mixtures to obtainsamples that are highly enriched in Structures A or B. The alcohol ofStructure B is the required composition for the group R_(a) (iii).

R_(f)OCFHCF₂O—(CH₂CH₂O)_(x)—CF₂CHFOR_(f)  (Structure A)

R_(f)OCFHCF₂O—(CH₂CH₂O)_(x)H  (Structure B)

Polyethylene glycols suitable for the use are commercially availablefrom Sigma-Aldrich, Milwaukee, Wis. The fluorinated vinyl ether used inthe above reaction is made by various methods. These methods includemaking fluorinated vinyl ethers by reacting a 2-alkoxypropionyl fluoridein a stationary bed of a metal carbonate, a tubular reactor filled withdried metal carbonate and equipped with a screw blade running throughthe tube, or a fluidized bed of metal carbonate. US Patent Application2007/0004938 describes a process to produce fluorinated vinyl ether byreacting a 2-alkoxypropionyl fluoride with a metal carbonate underanhydrous conditions in a stirred bed reactor at a temperature above thedecarboxylation temperature of an intermediate carboxylate to producefluorinated vinyl ether. Examples of fluorinated vinyl ethers suitablefor use include CF₃—O—CF═CF₂, CF₃CF₂—O—CF═CF₂, CF₃CF₂CF₂—O—CF═CF₂, andCF₃CF₂CF₂CF₂—O—CF═CF₂, each of which are available from E. I. du Pont deNemours and Company, Wilmington, Del.

The R_(a) group of Formula (iv) R_(f)OCFHCF₂O(C_(w)H_(2w))—wherein w isfrom about 3 to about 12, is prepared by the reaction of aperfluorohydrocarbonvinyl ether with a diol in the presence of an alkalimetal compound. Preferred ethers include those of formula R_(f)—O—CF═CF₂wherein R_(f) is a perfluoroalkyl of two to six carbons. The diol isused at about 1 to about 15 mols per mol of ether, preferably from about1 to about 5 mols per mol of ether. Suitable alkali metal compoundsinclude an alkali metal, alkali earth metal, alkali hydroxide, alkalihydride, or an alkali amide. Preferred are alkali metals such as Na, Kor Cs, or alkali hydrides such as NaH or KH. The reaction is conductedat a temperature of from about 40° C. to about 120° C. The reaction canbe conducted in an optional solvent, such as ether or nitrile.

The R_(a) group of Formula (v) R_(f)OCF(CF₃)CONH—CH₂CH₂—, is prepared bymaking a fluorinated alcohol of Formula 4:

wherein

R_(f) is a straight or branched perfluoroalkyl group having from about 2to about 6 carbon atoms, or a mixture thereof,

X³ is oxygen or X¹,

each X¹ is independently an organic divalent linking group having fromabout 1 to about 20 carbon atoms, optionally containing an oxygen,nitrogen, or sulfur, or a combination thereof,

G is F or CF₃,

A is an amide,

j′ is zero or positive integer,

X² is an organic linking group,

h′ is zero or one,

B is H,

and E is hydroxyl.

The compound of Formula 4 is prepared by reaction between aperfluorinated ester (prepared according to reported methods in U.S.Pat. No. 6,054,615 and U.S. Pat. No. 6,376,705 each herein incorporatedby reference) with a triamine or diamine alcohol with or withoutsolvent. The conditions of this reaction are dependent on structure ofthe ester. The reaction of alpha, alpha-difluorosubstituted ester withdiamine is conducted at a temperature of from about 5° C. to about 35°C. Suitable solvents for this reaction include tetrahydrofuran, methylisobutyl ketone, acetone, CHCl₃, CH₂Cl₂, or ether. The reaction of esterwithout alpha-fluorine substitution with diamine is conducted at atemperature of from about 90° C. to about 160° C., preferably at betweenabout 100° C. to about 140° C. Preferably no solvent is employed forthis reaction, but suitable solvents include chlorobenzene,dimethylformamide, or 2-methoxyethyl ether.

The compound of Formula 4 is also prepared by reaction between aperfluorinated acyl fluoride with a diamine alcohol or amine alcohol.This reaction is conducted at a temperature of from about −30° C. toabout 40° C., preferably at between about 5° C. to about 25° C. Suitablesolvents for this reaction include tetrahydrofuran, methyl isobutylketone, acetone, CHCl₃, CH₂Cl₂, or 2-methoxyethyl ether, diethyl ether.

The R_(a) group of Formula (vi), above,R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)—, is obtained bypreparation of fluoroalcohols of the formulaR_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)OH, wherein R_(f) is a C₂ toC₆ perfluoroalkyl, subscript h is 1 to about 6, and subscripts i, j, andk are each independently 1, 2, 3, or a mixture thereof. These alcoholsare prepared from oligomeric iodides (C_(n)F_(2n+1)C₂H₄I,C_(n)F_(2n+1)CH₂I or C_(n)F_(2n+1)I) wherein subscript n is an integerfrom 1 to about 6, using an oleum treatment and hydrolysis. It has beenfound, for example, that reacting with oleum (15% SO₃) at about 60° C.for about 1.5 hours, followed by hydrolysis using an iced dilute K₂SO₃solution, and then followed by heating to about 100° C. for about 30minutes gives satisfactory results. But other reaction conditions canalso be used. After being cooled to ambient room temperature, a solid isprecipitated, isolated and purified. For example, the liquid is thendecanted and the solid is dissolved in ether and washed with watersaturated with NaCl, dried over anhydrous Na₂SO₄, and concentrated anddried under vacuum. Other conventional purification procedures can beemployed.

Alternatively, the alcohols of formulaR_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)OH as defined above can beprepared by heating the oligomeric iodidesR_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)I wherein R_(f), andsubscripts h, i, j, and k are as defined above for the correspondingalcohol, with N-methylformamide to about 150° C. and holding for about19 hours. The reaction mixture is washed with water to give a residue. Amixture of this residue with ethanol and concentrated hydrochloric acidis gently refluxed (at about 85° C. bath temperature) for about 2.5hours. The reaction mixture is washed with water, diluted withdichloromethane, and dried over sodium sulfate. The dichloromethanesolution is concentrated and distilled at reduced pressure to give thealcohol. Optionally N,N-dimethylformamide can be used instead ofN-methylformamide. Other conventional purification procedures can alsobe employed.

The iodides of formula R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)I arepreferably prepared by oligomerization of C_(n)F_(2n+1)C₂H₄I,C_(n)F_(2n+1)CH₂I or C_(n)F_(2n+1)I wherein n is 1 to about 6 using amixture of ethylene and tetrafluoroethylene. The reaction can beconducted at any temperature from room temperature to about 150° C. witha suitable radical initiator. Preferably the reaction is conducted at atemperature of from about 40° to about 100° C. with an initiator whichhas about a 10 hour half-life in that range. The feed ratio of thestarting materials in the gas phase, that is the moles ofC_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I or C_(n)F_(2n+1)I wherein n is 1to about 6, versus the combined moles of ethylene andtetrafluoroethylene, can be used to control conversion of the reaction.This mole ratio is from about 1:3 to about 20:1, preferably from about1:2 to 10:1, more preferably from about 1:2 to about 5:1 The mole ratioof ethylene to tetrafluoroethylene is from about 1:10 to about 10:1,preferably from about 3:7 to about 7:3, and more preferably from about4:6 to about 6:4.

The present invention further comprises the unsaturated intermediatesused in the preparation of the surfactants of the present invention thatare formed prior to the addition of the sulfonic acid group. Theunsaturated intermediates have the structure of Formulae 2A, 2B, and 2C:

(R_(a)—O—CO—)₂Y  Formula 2A

R_(a)—O—CO—Y—CO—O—(CH₂CH₂)R_(f)  Formula 2B

R_(a)—O—CO—Y—CO—O—R  Formula 2C

wherein

R_(a) is the group

(i) R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—;

(ii) R_(f)OCF₂CF₂—(C_(g)H_(2g))—;

(iii) R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—;

(iv) R_(f)OCFHCF₂O(C_(w)H_(2w))—; (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g))—;or

(vi) R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k)

each R_(f) is independently C_(c)F_((2c+1));

c is 2 to about 6, preferably from 2 to 4, more preferably 4;

d is 1 to about 3, preferably from 1 to 2, more preferably 1;

g is 1 to 4, preferably from 1 to 3, more preferably 2;

v is 1 to about 4, preferably from 2 to 3, more preferably 2;

w is from about 3 to about 12, preferably from 4 to 6, more preferably4;

h is 1 to about 6, preferably from 1 to 3, more preferably 2;

i, j, and k are each independently 1, 2, or 3, or a mixture thereof,preferably 1 or 2, more preferably 1;

provided that the total number of carbon atoms in group (vi) is fromabout 8 to about 22;

Y is a linear or branched diradical having olefinic unsaturation of theformula

—C_(e)H_((2e−2))—

wherein

e is 2 or 3, preferably 2;

R is H or a linear or branched alkyl group C_(b)H_((2b+1))—; and

b is from 1 to about 18, preferably from 6 to 18.

Compounds of Formulae 2A, 2B, and 2C are prepared as discussed above forFormulae 1A, 1B, and 1C except that the sulfonation step is omitted.Compounds of Formula 2A, 2B, and 2C are also monomers that can bepolymerized alone or in admixture with other monomers to confer soil andwater repellency to the resulting polymers and to surfaces to which theresulting polymers are applied.

Preferred compounds of Formula 2A, 2B, and 2C are those wherein R_(a) isR_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—; R_(f)OCF₂CF₂—(C_(g)H_(2g))—;R_(f)—OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—; orR_(f)OCFHCF₂O(C_(w)H_(2w)O)—(C_(g)H_(2g))—. Also preferred are thosecompounds of Formula 2A, 2B and 2C wherein c is 3 or 4, or wherein Y isCH═CH, CH₂C(═CH₂), C(CH₃)═CH₂, CH═CHCH₂, or CH₂CH═CHCH₂. More preferredare those compounds wherein R_(a) is R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—;R_(f)OCF₂CF₂—(C_(g)H_(2g))—; R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—;or R_(f)OCFHCF₂O(C_(w)H_(2w)O)—(C_(g)H_(2g))—; d is 1, g is 1, R_(f) isC₃F₇ or C₄F, and Y is CH═CH, CH₂C(═CH₂), or C(CH₃)═CH₂. Also preferredare compounds of Formula 2B wherein R_(a) is C₄F₉CH₂CF₂CH₂CH₂ orC₃F₇CH₂CF₂CH₂CH₂ and R_(f) is (CF₂)₆F.

The compounds of Formula 2A, 2B and 2C are useful as intermediates toprepare partially fluorinated sulfonated surfactants, in particularthose of Formula 1A, 1B and 1C as previously defined.

The present invention further comprises a method of altering the surfacebehavior of a liquid, comprising adding to the liquid a compound ofFormulae 1A, 1B, and 1C, as defined above, in a wide variety ofapplications. The surfactants of Formula 1A, 1B, and 1C are typicallyused by simply blending with or adding to water, aqueous solutions, andaqueous emulsions. The surfactants of Formulae 1A, 1B, and 1C typicallylower surface and interfacial tensions and provide low critical micelleconcentrations. Examples of surface behavior alteration includeimprovements in the properties of wetting, penetration, spreading,leveling, flowing, emulsifying, stabilization of dispersions in liquids,repellency, releasing, lubricating, etching, and bonding.

Examples of such applications where low surface tension is requiredinclude coating compositions and aqueous and non-aqueous cleaningproducts, each for glass, wood, metal, brick, concrete, cement, naturaland synthetic stone, tile, synthetic flooring, laminates, paper, textilematerials, linoleum and other plastics, resins, natural and syntheticrubbers, fibers and fabrics, and paints; polymers; and waxes, finishes,leveling and gloss agents for floors, furniture, shoes, inks, andautomotive care. Wetting agent applications include wetting agents forcompositions containing herbicides, fungicides, weed killers, hormonegrowth regulators, parasiticides, insecticides, germicides,bactericides, nematocides, microbiocides, defoliants or fertilizers,therapeutic agents, antimicrobials, fluorochemical blood substitutes,textile treatment baths, and fiber spin finishes. Applications inpersonal care products include shampoos, conditioners, creme rinses,cosmetic products for the skin (such as therapeutic or protective creamsand lotions, oil and water repellent cosmetic powders, deodorants andantiperspirants), nail polish, lipstick, and toothpaste. Furtherapplications include fabric care products (such as stain pretreatmentsand/or stain removers for clothing, carpets and upholstery), and laundrydetergents. Other applications include rinse-aids (for car washes and inautomatic dishwashers), for oil well treatments (including drilling mudsand additives to improve tertiary oil well recovery), extreme pressurelubricants, lubricating cutting oil to improve penetration times,writing inks, printing inks, photography developer solutions, emulsionsfor fighting forest fires, dry chemical fire extinguishing agents,aerosol-type fire extinguishers, thickening agents to form gels forsolidifying or encapsulating medical waste, photoresists, developers,cleaning solutions, etching compositions, developers, polishers, andresist inks in the manufacturing, processing, and handling ofsemiconductors and electronics. The surfactants of the present inventioncan be incorporated into products that function as antifogging agentsfor glass surfaces and photography films, and as antistatic agents formagnetic tapes, phonograph records, floppy disks, disk drives, rubbercompositions, PVC, polyester film, and photography films, and as surfacetreatments for optical elements (such as glass, plastic, or ceramics).Other applications are in emulsifying agents, foaming agents, releaseagents, repellency agents, flow modifiers, film evaporation inhibitors,wetting agents, penetrating agents, cleaners, grinding agents,electroplating agents, corrosion inhibitors, soldering agents,dispersion aids, microbial agents, pulping aids, rinsing aids, polishingagents, drying agents, antistatic agents, antiblocking agents, bondingagents, and oil field chemicals.

The compounds of the present invention are also useful as foam controlagents in polyurethane foams, spray-on oven cleaners, foamed kitchen andbathroom cleansers and disinfectants, aerosol shaving foams, and intextile treatment baths. The surfactants of the present invention areuseful as emulsifying agents for polymerization, particularly offluoromonomers, as latex stabilizers, as mold release agents forsilicones, photoemulsion stabilizers, inorganic particles, and pigments.Such fluorosurfactants are also useful for supercritical carbon dioxideemulsions and dispersion of nanoparticles or pigments in water.

A low concentration of less than about 0.1%, preferably less than about0.01% by weight of a compound of Formulae 1A, 1B, or 1C in the liquid iseffective. Consequently, the surfactants of Formulae 1A, 1B, and 1C areuseful in a wide variety of end use applications.

The present invention further comprises compounds of Formula 5

R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—H  Formula 5

wherein

R_(f) is C_(c)F_((2c+1));

c is 2 to about 6, preferably from 2 to 4, more preferably 4; and

v is 2 to about 4, preferably from 2 to 3, more preferably 2.

Preferred compounds of Formula 5 are those wherein c is 3 or 4, g is 2,and v is 2 or 3. The compounds of Formula 5 are useful as intermediatesin making partially fluorinated sulfonated surfactants. In particular,Formula 5 compounds are useful in making surfactants of Formula 1A, 1Band 1C as previously defined.

The present invention further comprises a process for the preparation ofa compound of Formula 5

R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—H  Formula 5

wherein

R_(f) is C_(c)F_((2c+1));

c is 2 to about 6; and

v is 2 to about 4,

comprising contacting a compound of Formula 6

R_(f)—O—CF═CF₂  Formula 6

wherein R_(f) is C_(c)F_((2c+1)), and c is 2 to about 6,with a compound of Formula 7

HO—(CH₂CH₂O)_(v)—H  Formula 7

wherein v is 2 to about 4.

In the process of the present invention the compound of Formula 5 isprepared by the reaction of a perfluorohydrocarbonvinyl ether with adiol in the presence of an alkali metal compound. Preferred ethersinclude those of formula R_(f)—O—CF═CF₂ wherein R_(f) is aperfluoroalkyl of one to six carbons. Preferred diols include diethyleneglycol. The diol is used at about 1 to about 15 mols per mol of ether,preferably from about 1 to about 5 mols per mol of ether. Suitablealkali metal compounds include an alkali metal, alkali earth metal,alkali hydroxide, alkali hydride, or an alkali amide. Preferred arealkali metals such as Na, K or Cs or alkali hydrides such as NaH or KH.The reaction is conducted at a temperature of from about ambienttemperature to about 120° C., preferably from about 40° C. to about 120°C. The reaction can be conducted in an optional solvent, such as etheror nitrile. The process is useful to prepare alcohols of Formula 5 whichare used to prepare derivative compounds, such as surfactants.

The surfactants of the present invention of Formula 1A, 1B, and 1C, inmany cases, require less tetrafluoroethylene in their preparation whencompared to conventional fluorosurfactants made from Telomer B alcohols.While tetrafluoroethylene may be used in the R_(f) portion of theR_(a)—OH alcohol precursors when R_(a) is (ii)R_(f)OCF₂CF₂—(C_(g)H_(2g))—; (iii)R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—; (iv)R_(f)OCFHCF₂O(C_(w)H_(2w))—; or (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g));tetrafluoroethylene is not otherwise used in the preparation of thecompounds of Formula 1A, 1B or 1C or of Formula 2A, 2B or 2C. For thesurfactants of the present invention, some of the fluorine is replacedwith other atoms or monomers, compared to the typical perfluoroalkylgroups of 1 to 20 carbons in surfactants made from traditional Telomer Balcohols. So less tetrafluoroethylene is used in the preparation ofcompounds of Formula 1A, 1B and 1C or of Formula 2A, 2B and 2Ccontaining the R_(a) (i) and (vi) groups.

The monomer moieties replacing tetrafluoroethylene in most cases alsocontain a lower proportion of fluorine. Consequently, in many cases thesurfactants of the present invention are more fluorine efficient thanmany conventional surfactants. By “fluorine efficiency” is meant theability to use a minimum amount of fluorochemical to obtain a desiredsurface effect or surfactant properties, when applied to substrates, orto obtain better performance using the same level of fluorine.

MATERIALS AND TEST METHODS

The following materials and test methods were used in the Examplesherein.

All common organic and inorganic compounds were obtained fromSigma-Aldrich (Milwaukee Wis.) and used without purification. Theseincluded maleic anhydride, sodium hydrogen sulfite, toluene, hexane,p-toluene sulfonic acid, itaconic anhydride, citraconic anhydride,trans-glutaconic acid, trans-beta-hydromuconic acid, and other routinecompounds employed in the Examples.

SIMULSOL SL8: octyl/deceyl polyglucoside is available from KreglingerEurope, Antwerp, Belgium.

TRITON X100: p-tert-octylphenoxy polyethyl alcohol is available fromSigma-Aldrich, Saint Louis, Mo.

DOWANOL DB: 1-butoxy-2-ethoxyethane is available from Dow ChemicalCompany, Midland, Mi.

SOLKANE 365 MFC is 1,1,1,3,3-pentafluorobutane is available from SolvayFluorides, Thorofare N.J.

The following fluorinated chemicals are available from E. I. du Pont deNemours and Company, Wilmington Del.:

Perfluoro-2-methyl-3-oxahexanoyl fluoride,

Perfluorobutyl iodide,

Vinylidene fluoride,

Perfluoropropylvinyl ether, and

Perfluoroethylethyl iodide.

The following fluorinated chemicals were prepared as indicated below:

C₄F₉CH₂CF₂I and C₄F₉(CH₂CF₂)₂I were prepared by reacting perfluorobutyliodide and vinylidene fluoride as described by Balague, et al,“Synthesis of Fluorinated Telomers, Part 1, Telomerization of VinylideneFluoride with Perfluoroalkyl Iodides”, J. Fluorine Chem. (1995), 70(2),215-23. The specific telomer iodides are isolated by fractionaldistillation.

C₃F₇OCF₂CF₂I was prepared by reacting perfluoropropyl vinyl ether withiodine chloride and hydrofluoric acid with boron trifluoride as acatalyst as described by Viacheslav et al. in U.S. Pat. No. 5,481,028.

Test Method 1—Measurement of the Critical Micelle Concentration (CMC)and the Surface Tension Beyond CMC.

Surface tensions of aqueous surfactant solutions were measured atvarious weight percents in mN/m using a Kruss K11 Tensiometer (fromKruss USA, Charlotte, N.C.). Compounds having the lowest surface tensionhave the highest effectiveness.

The critical micelle concentration (CMC) is defined as the concentrationat which increased concentrations of surfactant essentially no longerreduce the surface tension. To determine CMC, the surface tension ismeasured as a function of surfactant concentration. Surface tension isthen plotted (abscissa) vs. log concentration (ordinate). The resultingcurve has a nearly horizontal portion at concentrations higher than theCMC and has a negative steep slope at concentrations less than the CMC.The CMC is the concentration at the intersection of the extrapolatedsteep slope and the extrapolated near horizontal line. The SurfaceTension beyond CMC is the value in the flat portion of the curve. TheCMC should be as low as possible to provide the lowest cost foreffective performance.

Test Method 2—Spreading on Cyclohexane

Test Method 2 is adapted from Stern et al. in WO1997046283A1, whereinsurfactants were applied to the surface of n-heptane to provide ascreening evaluation for Advance Fire Fighting Foams (AFFF). Cyclohexanewas used in Test Method 2 to replace the n-heptane used by Stern et al.Test Method 2 measures the ability of the surfactant solution to spreadacross the surface of a less dense flammable liquid. When the surfactantsolution spreads across the surface (“excellent” rating), a barrier isestablished between the flammable liquid and the air. If the surfactantsolution does not spread completely across the surface (“good” or “fair”rating depending on the extent of the partial spreading) the barrierbetween air and flammable liquid is incomplete. If the surfactantsolution sinks into the flammable liquid (“poor” rating), no barrierbetween air and flammable liquid is established.

A surfactant solution was prepared by combining fluorosurfactant (0.9g/L of active ingredient), hydrocarbon surfactant (either SIMULSOL SL8or TRITON X100; 2.4 g/L of active ingredient), butyl carbitol (DOWANOLDB; 4.2 g/L of active ingredient), and mixed thoroughly. A Petri dish(11.5 cm diameter) was filled about half-way with 75 mL of cyclohexane.After the surface of the cyclohexane had completely calmed (about 1minute), 100 microliters of the solution of fluorosurfactant,hydrocarbon surfactant, butyl carbitol, and water was deposited dropwisewith a micropipette beginning at the center of the Petri dish andoutwardly along a radial line to the outer edge of the Petri dish. Thetimer was started.

In poor performing formulations, the surfactant solution “sinksimmediately” below the cyclohexane.

In fair performing formulations, the surfactant solution merely “floats”on the surface of the cyclohexane without sinking.

In good performing formulations, the surfactant spreads across thesurface of the cyclohexane. The time was noted when the extent of thespreading of the surfactant solution across the surface of thecyclohexane ceased and the extent of the surface coverage (<100%) atthat point was recorded.

In excellent performing formulations, the surfactant solution rapidlyspreads across the entire surface of the cyclohexane. In excellentperforming formulations, the time was noted when extent of the spreadingof the surfactant solution first covered the entire surface (100%).

EXAMPLES Example 1

A mixture of ethanolamine (13 g, 28 mmol) and ether (30 mL) was cooledto 15° C. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33 g in ether 50mL) was added dropwise to keep the reaction temperature below 25° C.After the addition, the reaction mixture was stirred at room temperaturefor one hour. The solid was removed by filtration and the filtrate waswashed with hydrochloric acid (0.5N, 30 mL), water (2 times 30 mL),sodium hydrogen carbonate solution (0.5N, 20 mL), water (30 mL), andsodium chloride solution (saturated, 20 mL). It was then concentratedand dried in vacuum over night at room temperature to give a white solid35 g, yield 95%. The product was analyzed using ¹HNMR and the structureconfirmed as is N-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethanol,C₃F₇OCF(CF₃)CONHCH₂CH₂OH.

A mixture of maleic anhydride (0.60 g, 6.1 mmol),C₃F₇OCF(CF₃)CONHCH₂CH₂OH (4.5 g, 12 mmol, prepared as described above),p-toluenesulfonic acid monohydrate (0.12 g) and toluene (50 mL) wasstirred continuously and heated to reflux under nitrogen. Thetemperature was maintained at 111° C. for approximately 22 h until 90%of water was removed azeotropically with the aid of a Dean-Stark trap. Aliquid chromatography/mass spectrum (LC/MS) was taken to show thecompletion to the diester. The solution was separated and extracted withtwo washings of 5% sodium bicarbonate solution. The combined organicextracts were dried over anhydrous magnesium sulfate (MgSO₄) and thentoluene was removed by rotary evaporation. The yellow oil (3.12 g, 61.9%yield, 90% purity) was analyzed by 1 HNMR and LC/MS to confirm thestructure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)CH═CHC(O)OCH₂CH₂NHC(O)—CF(CF₃)OC₃F₇.

Example 2

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH bp 54-57° C. at 2 mmHg (267 Pa).

The esterification procedure of Example 1 was used to makeDi(1H,1H,2H,2H,4H,4H-perfluorooctyl) maleate (7.76 g, 95% yield, 95%purity) by the reaction of maleic anhydride (1.07 g, 11 mmol).C₄F₉CH₂CF₂CH₂CH₂OH (7.13 g, 22 mmol, prepared as described above) andp-toluenesulfonic acid monohydrate (0.21 g, 1.1 mmol) in 50 mL oftoluene at 111° C. for 40 h. The pale yellow product was analyzed by 1HNMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)—CH═CH—C(O)OCH₂CH₂CF₂CH₂C₄F₉.

Example 3

Ethylene (56 g) was introduced to an autoclave charged withC₄F₉(CH₂CF₂)₂I (714 g) and d-(+)-limonene (3.2 g), and the reactorheated at 240° C. for 12 hours. The product was isolated by vacuumdistillation to provide C₄F₉(CH₂CF₂)₂CH₂CH₂I. A mixture ofC₄F₉(CH₂CF₂)₂CH₂CH₂I (10 g, 0.02 mol) and N-methylformamide (8.9 mL,0.15 mol) was heated to 150° C. for 26 hours. The mixture was cooled to100° C., followed by the addition of water to separate the crude ester.Ethyl alcohol (3 mL) and p-toluene sulfonic acid (0.09 g) were added andthe mixture stirred at 70° C. for 0.25 hours. Ethyl formate and ethylalcohol were removed by distillation to give a crude product. The crudeproduct was dissolved in ether, washed with 10 wt % aqueous sodiumsulfite, water and brine, in turn, and dried over magnesium sulfate.Distillation provided the product C₄F₉(CH₂CF₂)₂CH₂CH₂OH (6.5 g, 83%yield): bp 94-95° C. at 2 mm Hg (266 Pa).

Maleic anhydride (0.65 g, 6.7 mmol), C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OH (4.37 g,1.333*10⁻² mol, prepared as described above), p-toluenesulfonic acidmonohydrate (0.13 g, 0.67 mmol) and toluene (50 mL) were mixed togetherand heated to reflux at 110° C. for 48 h. The work-up was carried out asin Example 1. The resulting pale yellow liquid (2.90 g, 51.4%yield, >99% purity) was analyzed by ¹H NMR and LC/MS to confirm thestructure asC₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CH═CH—C(O)OCH₂CH₂CF₂CH₂CF₂CH₂C₄F₉.

Example 4

C₃F₇OCF₂CF₂I (100 g, 0.24 mol) and benzoyl peroxide (3 g) were chargedto a pressure vessel under nitrogen. A series of three vacuum/nitrogengas sequences was then executed at −50° C. and ethylene (18 g, 0.64 mol)was introduced. The vessel was heated for 24 hour at 110° C. Theautoclave was cooled to 0° C. and opened after degassing. Then theproduct was collected in a bottle. The product was distilled giving 80 gof C₃F₇OCF₂CF₂CH₂CH₂I in 80% yield. The boiling point was 56˜60° C. at25 mm Hg (3.3 kPa).

A mixture of C₃F₇OCF₂CF₂CH₂CH₂I (300 g, 0.68 mol, prepared as describedabove) and N-methyl-formamide (300 mL), was heated to 150° C. for 26 h.Then the reaction was cooled to 100° C., followed by the addition ofwater to separate the crude ester. Ethyl alcohol (77 mL) and p-toluenesulfonic acid (2.59 g) were added to the crude ester, and the reactionwas stirred at 70° C. for 15 minutes. Then ethyl formate and ethylalcohol were distilled out to give a crude product. The crude productwas dissolved in ether, washed with aqueous sodium sulfite, water, andbrine in turn, then dried over magnesium sulfate. The product was thendistilled to give 199 g of C₃F₇OCF₂CF₂CH₂CH₂OH in 85% yield. The boilingpoint was 71˜73° C. at 40 mm Hg (5333 Pa).

A similar procedure as Example 1 was conducted. Maleic anhydride (0.66g, 6.8 mmol), C₃F₇OCF₂CF₂CH₂CH₂OH (4.46 g, 14 mmol, prepared asdescribed above), p-toluenesulfonic acid monohydrate (0.13 g, 0.68 mmol)and toluene (50 mL) were mixed together and refluxed for 50 h at 112° C.The pale yellow crude product (4.12 g, 82.4%, >99% purity) was analyzedby ¹H NMR and LC/MS to confirm the structure asC₃F₇OCF₂CF₂CH₂CH₂OC(O)CH═CHC(O)OCH₂CH₂NHC(O)CF(CF₃)O C₃F₇.

Example 5

In a dry box, a 500 mL Pyrex bottle was charged with diethylene glycol(99%, Aldrich Chemical Company) (175 mL, 1.84 mole) and 80 mL ofanhydrous tetrahydrofuran (Aldrich Sure/Seal™). NaH (3.90 g, 0.163 mole)was added slowly with magnetic stirring until the completion of hydrogenevolution. The capped bottle was removed from the drybox, and thesolution was transferred to a 400 mL metal shaker tube in a nitrogenfilled glovebag. The shaker tube was cooled to an internal temperatureof −18° C., shaking was started, and perfluoropropylvinyl ether (PPVE,41 g 0.145 mole) was added from a metal cylinder. The mixture wasallowed to warm to room temperature and was shaken for 20 h. Thereaction mixture was combined with a duplicate reaction run in aseparate 400 mL shaker tube. The combined reaction mixtures were addedto 600 mL of water, and this mixture was extracted with 3×200 mL ofdiethyl ether in a separatory funnel. The ether extracts were dried overMgSO₄, filtered, and concentrated in vacuo on a rotary evaporator togive a liquid (119.0 g) ¹H NMR in CD₃OD, and analysis by gaschromatography both showed a small amount of diethylene glycol. Thismaterial was dissolved in 150 mL of diethyl ether and extracted withwater (3×150 mL) in a separatory funnel. The ether layer was dried overMgSO₄, filtered, and concentrated in vacuo on a rotary evaporator athigh vacuum to give a liquid (99.1 g) ¹H NMR(C₆D₆, ppm downfield of TMS)shows 97 mole % desired mono-PPVE adduct: 1.77 (broad s, OH), 3.08-3.12(m, OCH₂CH ₂OCH ₂CH₂OH), 3.42 (t, OCH₂CH₂OCH₂CH ₂OH), 3.61 (t, OCH₂CH₂OCH₂CH₂OH), 5.496 (doublet of triplets, ²J_(H—F)=53 HZ, ³J_(H—F)=3Hz OCF₂CHFOC₃F₇), and 3 mole % of the bis PPVE adduct: 5.470 (doublet oftriplets, ²J_(H—F)=53 HZ, ³J_(H—F)=3 Hz,C₃F₇OCHFCF₂OCH₂CH₂OCH₂CH₂OCF₂CHFOC₃F₇) The other peaks for the bis PPVEadduct overlap with the mono PPVE adduct.

A mixture of maleic anhydride (0.59 g, 6.1 mmol),C₃F₇OCHFCF₂OCH₂CH₂OCH₂CH₂OH (4.5 g, 12 mmol, prepared as above,p-toluenesulfonic acid monohydrate (0.12 g, 0.61 mmol) and toluene (50mL) were stirred continuously together and heated to reflux at 114° C.for a period of 25 h. The reaction was confirmed to be completed throughLC/MS and the removal of water. The work-up as in Example 1 was carriedout to produce a pale yellow liquid (4.48 g, 90.0% yield, 87% purity. ¹HNMR and LC/MS were used to confirm the complete conversion to thediester and the structure asC₃F₇OCFHCF₂OCH₂CH₂OCH₂CH₂OC(O)CH═CHC(O)OCH₂CH2O—CH₂CH₂OCF₂CFHOC₃F₇.

Example 6

A one-gallon reactor was charged with perfluoroethylethyl iodide (850g). After cool evacuation, ethylene and tetrafluoroethylene in a ratioof 27:73 were added until pressure reached 60 psig (414 kPa). Thereaction was then heated to 70° C. More ethylene and tetrahydrofuran ina 27:73 ratio were added until pressure reached 160 psig (1.205 MPa). Alauroyl peroxide solution (4 g lauroyl peroxide in 150 gperfluoroethylethyl iodide) was added at a 1 mL/min. rate for 1 hour.Gas feed ratio was adjusted to 1:1 of ethylene and tetrafluoroethyleneand the pressure was kept at 160 psig (1.205 MPa). After about 67 g ofethylene was added, both ethylene and tetrafluoroethylene feeds werestopped. The reaction was heated at 70° C. for another 8 hours. Thevolatiles were removed by vacuum distillation at room temperature. Asolid of oligomer ethylene-tetrafluoroethylene iodidesC₂F₅(CH₂)₂[(CF₂CF₂)(CH₂CH₂)]_(k)—I (773 g) wherein k is a mixture of 2and 3 in about a 2:1 ratio was obtained.

An oligomer iodide mixture, prepared as described above (46.5 g) withoutseparation of the iodides was mixed with N-methylformamide (NMF, 273 mL)and heated to 150° C. for 19 h. The reaction mixture was washed withwater (4×500 mL) to give a residue. A mixture of this residue, ethanol(200 mL), and concentrated hydrochloric acid (1 mL) was gently refluxed(85° C. bath temperature) for 24 h. The reaction mixture was poured intowater (300 mL). The solid was washed with water (2×75 mL) and driedunder vacuum (2 torr, 267 Pa) to give a solid, 24.5 g. About 2 g ofproduct was sublimed. The total yield of oligomer alcoholsC₂H₅(CH₂)_(h)[(CF₂CF₂)(CH₂CH₂)]_(k)—OH wherein k is a mixture of 2 and 3in about a 2:1 ratio was 26.5 g.

A mixture of maleic anhydride (1.74 g, 18 mmol) andC₂F₅(CH₂)₂[(CF₂CF₂)(CH₂CH₂)]_(k)—OH (6.26 g) were stirred continuouslytogether and heated to 70° C. The reaction was carried out neat for 45 hand a gas chromatogram (GC) was taken at several intervals to notice thedisappearance of reactants and the introduction of the half acid/ester.C₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_(k)—OC(O)CH═CHC(O)OH. The half acid/ester(4.75 g, 9.7 mmol), C₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_(k)—OH (3.80 g, 9.7mmol), and p-toluenesulfonic acid monohydrate (0.12 g, 0.97 mmol) wereheated to reflux in toluene (50 mL) at 114° C. for 19 h. The product wasisolated using extraction with CH₃CN (3×100 mL), concentration,extraction with tetrahydrofuran, concentration, and drying was toproduce the yellow/orange solid product (7.46 g, 93.3% yield, 97%),which was analyzed by ¹H NMR and LC/MS to confirm the structure asC₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]kOOC(O)CH═CHC(O)O[(CH₂CH₂)—(CF₂CF₂)]k-CH₂CH₂C₂F₅wherein k is a mixture of 2 and 3.

Example 7

A mixture of ethanolamine (13 g, 28 mmol) and ether (30 mL) was cooledto 15° C. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33 g in ether 50mL) was added dropwise to keep the reaction temperature below 25° C.After the addition, the reaction mixture was stirred at room temperaturefor one hour. The solid was removed by filtration and the filtrate waswashed with hydrochloric acid (0.5N, 30 mL), water (2 times 30 mL),sodium hydrogen carbonate solution (0.5N, 20 mL), water (30 mL), andsodium chloride solution (saturated, 20 mL). It was then concentratedand dried in vacuum over night at room temperature to give a white solid35 g, yield 95%. Analysis by ¹H NMR and F NMR showed the product wasN-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethanol,C₃F₇OCF(CF₃)CONHCH₂CH₂OH.

Itaconic anhydride (0.67 g, 6.0 mmol), C₃F₇OCF(CF₃)CONHCH₂CH₂OH (4.44 g,12 mmol, prepared as described above), p-toluenesulfonic acidmonohydrate (0.11 g, 0.60 mmol), and toluene (50 mL) were stirredcontinuously and heated to reflux at 111° C. for a period of 25 h. Thetoluene was decanted off to leave a yellow, viscous solid. The productwas firstly air-dried and then placed in a vacuum oven for 2 h. Theproduct (3.62 g, 72.4%, 65% purity) was analyzed by ¹H NMR and LC/MS toconfirm complete conversion and the structure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)CH₂C(═CH₂)C(O)OCH₂CH₂—NHC(O)CF(CF₃)OC₃F₇.

Example 8

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH bp 54-57° C. at 2 mmHg (267 Pa).

Itaconic anhydride (0.75 g, 6.7 mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.37 g, 13mmol, prepared as described above), p-toluenesulfonic acid monohydrate(0.13 g, 0.67 mmol) and toluene (50 mL) were refluxed for a period of 19h at a temperature of 113° C. The resulting pale yellow liquid (4.53 g,90.6% yield, 72% purity) was analyzed by ¹H NMR and LC/MS to confirm thestructure as C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂C(═CH₂)C(O)OCH₂CH₂CF₂CH₂C₄F₉.

Example 9

A mixture of ethanolamine (13 g, 28 mmol) and ether (30 mL) was cooledto 15° C. Perfluoro-2-methyl-3-oxahexanoyl fluoride (33 g in ether 50mL) was added dropwise to keep the reaction temperature below 25° C.After the addition, the reaction mixture was stirred at room temperaturefor one hour. The solid was removed by filtration and the filtrate waswashed with hydrochloric acid (0.5N, 30 mL), water (2 times 30 mL),sodium hydrogen carbonate solution (0.5N, 20 mL), water (30 mL), andsodium chloride solution (saturated, 20 mL). It was then concentratedand dried in vacuum over night at room temperature to give a white solid35 g, yield 95%. Analysis by ¹H NMR and F NMR showed the product wasN-(perfluoro-2-methyl-3-oxahexanoyl)-2-aminoethanol,C₃F₇OCF(CF₃)CONHCH₂CH₂OH.

Citraconic anhydride (0.67 g, 6.0 mmol), C₃F₇OCF(CF₃)CONHCH₂CH₂OH (4.44g, 12 mmol, prepared as described above), p-toluenesulfonic acidmonohydrate (0.11 g, 0.60 mmol) and toluene (50 mL) were added togetherand heated to reflux at 111° C., with continual stirring, for 40 h.There were two noticeable solid materials present within the toluenesolution. The pinkish solid was removed and the white solid was vacuumfiltered. Both materials were analyzed by LC/MS, which confirmed thatthe pinkish solid was the product and the white solid was unreactedalcohol (1.22 g). The product (2.98 g, 59.6% yield, 65% purity) wasanalyzed by ¹H NMR and LC/MS to confirm the structure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)—C(CH₃)═CH₂C(O)OCH₂CH₂NHC(O)CF(CF₃)OC₃F₇.

Example 10

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH: bp 54-57° C. at 2 mmHg (267 Pa).

Citraconic anhydride (0.75 g, 6.7 mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.37 g,13.3 mmol, prepared as described above), p-toluenesulfonic acidmonohydrate (0.13 g), and toluene (50 mL) were refluxed for about 46 hat 112° C., after which only the diester was observed in the LC/MSanalysis. The work-up was carried out as in example 1 to give a paleyellow liquid (2.98 g, 59.6% yield, >99% purity) which was analyzed by¹H NMR and LC/MS to confirm the diester structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)C(CH3)═CH₂C(O)OCH₂CH₂CF₂CH₂C₄F₉.

Example 11

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH: bp 54-57° C. at 2 mmHg (267 Pa).

Trans-glutaconic acid (0.87 g, 6.7 mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.37 g, 13mmol, prepared as described above), p-toluenesulfonic acid monohydrate(0.13 g, 0.67 mmol) and toluene (50 mL) were stirred continuouslytogether and heated to reflux at 111° C. for 24 h. The work-up procedurewas carried out as in Example 1. The resulting white solid (2.52 g,50.4% yield, 80% purity) was dried in a vacuum oven and analyzed by ¹HNMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH═CHCH₂C(O)OCH₂CH₂CF₂CH₂C₄F₉.

Example 12

Ethylene (56 g) was introduced to an autoclave charged withC₄F₉(CH₂CF₂)₂I (714 g) and d-(+)-limonene (3.2 g), and the reactorheated at 240° C. for 12 hours. The product was isolated by vacuumdistillation to provide C₄F₉(CH₂CF₂)₂CH₂CH₂I. A mixture ofC₄F₉(CH₂CF₂)₂CH₂CH₂I (10 g, 0.02 mol) and N-methylformamide (8.9 mL,0.15 mol) was heated to 150° C. for 26 hours. The mixture was cooled to100° C., followed by the addition of water to separate the crude ester.Ethyl alcohol (3 mL) and p-toluene sulfonic acid (0.09 g) were added andthe mixture stirred at 70° C. for 0.25 hours. Ethyl formate and ethylalcohol were removed by distillation to give a crude product. The crudeproduct was dissolved in ether, washed with 10% by weight aqueous sodiumsulfate, water and brine, in turn, and dried over magnesium sulfate.Distillation provided the product C₄F₉(CH₂CF₂)₂CH₂CH₂OH (6.5 g, 83%yield): bp 94-95° C. at 2 mm Hg (266 Pa).

Trans-glutaconic acid (0.75 g, 5.8 mmol), C₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OH (4.54g, 12 mmol, prepared as described above), p-toluenesulfonic acidmonohydrate (0.11 g, 0.58 mmol) and toluene (50 mL) were stirredcontinuously together and heated to reflux at 111° C. for a period of 16h. The progress was monitored by LC/MS and the removal of waterazeotropically. The orange/yellow solid was filtered and washed with 5%sodium bicarbonate solution (50 mL). The filtrate was separated and theorganic layer was washed with 5% sodium bicarbonate solution (50 mL),and then with deionized water (50 mL). The combined organic extractswere dried over anhydrous MgSO₄ and the toluene was then concentrated(140.30 mmHg, 67° C.). The orange solid (4.14 g, 81.5% yield, 85%purity) was dried in a vacuum oven and analyzed by ¹H NMR and LC/MS toconfirm the structure asC₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CH═CHCH₂C(O)O—CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉.

Example 13

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH: bp 54-57° C. at 2 mmHg (267 Pa).

A melt reaction was undertaken by reacting maleic anhydride (2.00 g, 20mmol) with C₄F₉CH₂CF₂CH₂CH₂OH (6.69 g, 20 mmol, prepared as describedabove). The reaction was sustained at 70° C. for a period of 34 h,during which aliquots were taken for GC analysis. The white solid halfacid/ester (8.02 g, 92.3% yield, >98% purity) was analyzed by ¹H NMR andLC/MS to confirm the structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)CH═CHC(O)OH.

Example 14

The maleate, prepared as described in Example 13, (6.68 g, 17 mmol),p-toluenesulfonic acid monohydrate (0.30 g, 1.7 mmol) and hexyl alcohol(1.60 g, 17 mmol) were mixed together along with toluene (50 mL). Themixture was stirred continuously together and heated to reflux at 114°C. for 19 h. The work-up procedure as in example 1 was conducted toproduce a clear liquid (7.14 g, 89.3% yield, 98% purity), that wasanalyzed by ¹H NMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH═CHC(O)O—(CH₂)₆H.

Example 15

The maleate, prepared as described in Example 13, (4.41 g, 10 mmol),p-toluenesulfonic acid monohydrate (0.20 g, 1.0 mmol) and C₆F₁₃CH₂CH₂OH(3.77 g, 10 mmol) were added together along with toluene (50 mL). Thecontents were refluxed for 19 h at 114° C. and the work-up procedure wascarried out as in Example 1. The pale yellow liquid (5.78 g, 72.3%yield, 90% purity) was analyzed by ¹H NMR and LC/MS to confirm theformation of the mixed diester and the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH═CHC(O)OCH₂CH₂(CF₂)₆F.

Example 16

The maleate, prepared as described in Example 1, (2.62 g, 3.2 mmol) andisopropyl alcohol (IPA, 31 g) were added together at 50° C. until themixture was dissolved; about 10 minutes. Aqueous sodium bisulfite (0.17g, 1.6 mmol) was dissolved in deionized water (8 mL) and added dropwiseto the isopropyl alcohol solution, which was then heated to reflux (86°C.) for 26 h. The isopropyl alcohol and water were removed by rotaryevaporation followed by drying in a vacuum oven at 50° C. to generate aviscous yellow liquid (1.70 g, 57.6% yield, 75% purity), which wasconfirmed to be the diester sulfonate by ¹H NMR and LC/MS analyses toconfirm the structure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O—CH₂CH₂NHC(O)CF(CF₃)OC₃F₇.

The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1; the results are shown in Table 2.

Example 17

The maleate, prepared as described in Example 2, (7.74 g, 11 mmol) andisopropyl alcohol (31 g) were stirred continuously together. Thetemperature was raised to 61° C. and then a solution of sodium bisulfite(1.09 g, 11 mmol), dissolved in deionized water (53 mL), was addeddropwise. The mixture was heated to reflux at an elevated temperature of82° C. for 24 h. The solution was concentrated to remove the isopropylalcohol/water solution. The remaining pale yellow liquid was driedovernight in an oven to produce a white solid (6.96 g, 78.8% yield, 98%purity) and was then analyzed by ¹H NMR and LC/MS to confirm thestructure as C₄F₉CH₂CF₂CH₂CH₂OC(O)—CH₂CH(SO₃Na)C(O)O—CH₂CH₂CF₂CH₂C₄F₉.The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1, with results shown in Table 2, and spreading oncyclohexane by Test Method 2, with results shown in Table 3.

Example 18

The maleate, prepared as described in Example 3, (2.88 g, 3.3 mmol) andisopropyl alcohol (31 g) were stirred continuously at 82° C., with theaddition of aqueous sodium bisulfite (1.54 g, 15 mmol), dissolved indeionised water (20 mL), for 28 h. The white solid (2.58 g, 80.1%yield, >95% purity) was collected by concentrating the isopropylalcohol/water solution and then dried in a vacuum oven overnight. Theproduct was analyzed by ¹H NMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O—CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉. Theproduct was evaluated for CMC and surface tension beyond the CMC by TestMethod 1, with results shown in Table 2, and spreading on cyclohexane byTest Method 2, with results shown in Table 3.

Example 19

The maleate, prepared as described in Example 4, (4.10 g, 5.5 mmol),isopropyl alcohol (31 g) and aqueous sodium bisulfite (0.28 g, 2.8 mmol)dissolved in deionized water (14 mL) were stirred continuously for 18 hat a temperature of 82° C. The white solid (3.36 g, 71.9% yield, >95%purity) was collected by rotary evaporating the isopropyl alcohol/watersolution and then the product was dried in a vacuum oven. The productwas analyzed by ¹H NMR and LC/MS to confirm conversion to the diestersulfonate and the structure asC₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O—CH₂CH₂CF₂CF₂OC₃F₇. The productwas evaluated for CMC and surface tension beyond the CMC by Test Method1, with results shown in Table 2, and spreading on cyclohexane by TestMethod 2, with results shown in Table 3.

Example 20

The maleate, prepared as described in Example 5, (1.49 g, 1.8 mmol),isopropyl alcohol (31 g) and aqueous sodium bisulfite (0.29 g, 2.8 mmol)dissolved in deionised water (14 mL) were mixed together and refluxedfor 27 h at 82° C. The isopropyl alcohol was concentrated and the whitesolid (1.46 g, 87.1% yield, >97% purity) obtained was dried in a vacuumoven and analyzed by ¹H NMR and LC/MS to confirm the structure asC₃F₇OCFHCF₂OCH₂CH₂OCH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O—CH₂CH₂OCH₂CH₂OCF₂CFHOC₃F₇.The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1, with results shown in Table 2, and spreading oncyclohexane by Test Method 2, with results shown in Table 3.

Example 21

The maleate, prepared as described in Example 6, (7.54 g, 8.7 mmol) andisopropyl alcohol (31 g) were heated to 50° C. until the solid haddissolved in solution. A solution of aqueous sodium bisulfite (0.91 g,8.7 mmol) dissolved in deionized water (43 mL) was transferred to themixture and the contents were refluxed at 82° C. for 20 h. The isopropylalcohol/water solution was removed by rotary evaporation to attain theorange/brown solid (7.22 g, 87.3% yield, 92% purity). The product wasanalyzed by ¹H NMR and LC/MS to confirm the structure asC₂F₅CH₂CH₂[(CF₂CF₂)(CH₂CH₂)]_(k)OOC(O)CH═CHC(O)O—[(CH₂CH₂)(CF₂CF₂)]_(k)CH₂CH₂C₂F₅,wherein k is a mixture of 2 and 3 in a 2:1 ratio. The product wasevaluated for CMC and surface tension beyond the CMC by Test Method 1;the results are shown in Table 2.

Example 22

The itaconate, prepared as described in Example 7, (3.60 g, 4.3 mmol)and isopropyl alcohol (31 g) were stirred continuously together. Anaqueous solution of sodium bisulfite (0.45 g, 4.3 mmol) dissolved indeionized water (21 mL) was added slowly to the solution and thetemperature was raised to 82° C. for 23 h. The isopropyl alcohol/waterwas concentrated to leave the yellow gel-like product (3.73 g, 92.1%yield, 75% purity), which was placed in a vacuum oven overnight analyzedby ¹H NMR and LC/MS to confirm the structure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O—CH₂CH₂NHC(O)CF(CF₃)OC₃F₇.The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1, with results shown in Table 2, and spreading oncyclohexane by Test Method 2, with results shown in Table 3.

Example 23

The itaconate, prepared as described in Example 8, (2.00 g, 2.7 mmol),isopropyl alcohol (31 g) and aqueous sodium bisulfite (0.28 g, 2.7 mmol)dissolved in deionized water (14 mL) were refluxed for 22 h at 82° C.The white solid (precipitate) was filtered off and washed with deionizedwater (50 mL) to remove unreacted NaHSO₃. The white dry solid (2.11 g,91.5% yield, >95% purity) was analyzed by ¹H NMR and LC/MS to confirmthe structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)OCH₂CH₂CF₂CH₂C₄F₉.The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1, with results shown in Table 2, and spreading oncyclohexane by Test Method 2, with results shown in Table 3.

Example 24

The citraconate, prepared as described in Example 9, (2.96 g, 3.5 mmol),and isopropyl alcohol (31 g) were stirred continuously together andheated to reflux. A solution of aqueous sodium bisulfite (0.37 g, 3.5mmol) dissolved in deionized water (18 mL) was added dropwise to themixture. The solution was maintained at 82° C. for 23 h. The solutionwas concentrated and two noticeable layers were observed. The small toplayer was yellow in colour and the bottom was white. Each layer wasanalyzed by 1 HNMR, which confirmed that the top layer was likely to beimpurities. The product was tested in isopropyl alcohol and also inwater, and the alcohol was also similarly tested. The results indicatedthat the product was soluble in water but insoluble in isopropylalcohol, and the opposite was true for the alcohol. Therefore, if theimpurity layer contained some alcohol this would be removed byfiltration when water was added. If any of the starting acid remainedthis would not affect the surface tension results. The bottom layer(2.62 g, 78.8% yield, 85% purity) was analyzed by ¹H NMR and LC/MS toconfirm the structure asC₃F₇OCF(CF₃)C(O)NHCH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O—CH₂CH₂NHC(O)CF(CF₃)OC₃F₇.

The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1; the results are shown in Table 2.

Example 25

The citraconate, prepared as described in Example 10, (2.70 g, 3.6 mmol)and isopropyl alcohol (31 g) were mixed together at 50° C. untildissolved; about 10 minutes. Aqueous sodium bisulfite (1.54 g, 14.8mmol) was dissolved in deionized water (15 mL) and added dropwise to theisopropyl alcohol solution, which was then heated to about 82° C. forabout 22 h. The isopropyl alcohol and water were removed by rotaryevaporation followed by drying in a vacuum oven at 50° C. to give anoff-white solid (1.56 g, 50.8% yield, Purity: >99%), which was analyzedby ¹H NMR and LC/MS to confirm the formation of the diester sulfonateand the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)—C(O)OCH₂CH₂CF₂CH₂C₄F₉. The product wasevaluated for CMC and surface tension beyond the CMC by Test Method 1,with results shown in Table 2, and spreading on cyclohexane by TestMethod 2, with results shown in Table 3.

Example 26

The trans-glutaconate, prepared as described in Example 11, (2.52 g, 3.4mmol) was added to isopropyl alcohol (31 g) and heated to 60° C. At thispoint a solution of sodium bisulfite (0.31 g, 3.0 mmol) dissolved indeionized water (15 mL) was added dropwise, and the temperature wasraised to 82° C. for 22 h. The pale yellow solid (2.26 g, 78.8% yield,80% purity) was analyzed by ¹H NMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)OCH₂CH₂CF₂CH₂—C₄F₉. The product wasevaluated for CMC and surface tension beyond the CMC by Test Method 1;the results are shown in Table 2.

Example 27

The trans-glutaconate, prepared as described in Example 12, (4.08 g, 4.6mmol) was added to isopropyl alcohol (31 g) and heated to 50° C. Asolution of sodium bisulfite (0.31 g, 3.0 mmol) dissolved in deionizedwater (15 mL) was added dropwise to the solution and the mixture washeated to 82° C. for 23 h. The yellow solid (3.94 g, 86.3% yield, 90%purity) was collected by rotary evaporating the isopropyl alcohol/watersolution and analyzed by ¹H NMR and LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CF₂CH₂CH₂OC(O)C₃H₅(SO₃Na)C(O)O—CH₂CH₂CF₂CH₂CF₂CH₂C₄F₉.

The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1; the results are shown in Table 2.

Example 28

The maleate, prepared as described in Example 13, (4.20 g, 9.4 mmol) andisopropyl alcohol (31 g) were heated to approximately 50° C. to allowfor the solid to dissolve in solution. Aqueous sodium bisulfite (0.99 g,9.4 mmol) dissolved in deionized water (47 mL) was transferred to thesolution and the contents were refluxed for 22 h at 82° C. The isopropylalcohol/water solution was rotary evaporated to leave the white solid(4.14 g, 82.8% yield, 90% purity) that was analyzed by ¹H NMR and LC/MSto confirm the structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)OH. Theproduct was evaluated for CMC and surface tension beyond the CMC by TestMethod 1; the results are shown in Table 2.

Example 29

The mixed diester, prepared as described in Example 14, (7.10 g, 13.9mmol) and isopropyl alcohol (32 g) were stirred continuously togetherand heated to 50° C. until the two liquids became miscible. Aqueoussodium bisulfite (1.45 g, 13.9 mmol) dissolved in deionized water (70mL) was transferred to the mixture and the contents were refluxed for 22h at 82° C. The isopropyl alcohol/water solution was evaporated off andthe white gel product (6.26 g, 73.3% yield, 98% purity) was dried invacuum oven for 2 h. The product was analyzed by ¹H NMR and LC/MS toconfirm the structure as C₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)O(CH₂)₆H.The product was evaluated for CMC and surface tension beyond the CMC byTest Method 1, with results shown in Table 2, and spreading oncyclohexane by Test Method 2, with results shown in Table 3.

Example 30

The mixed diester, prepared as in Example 15 (5.78 g, 7.5 mmol) andisopropyl alcohol (31 g) were added together and heated to 60° C. for 10minutes. A solution of sodium bisulfite (0.78 g, 7.5 mmol) dissolved indeionized water (37 mL) was added to the solution and the mixture washeated to reflux at 82° C. for a period of 20 h. The isopropylalcohol/water solution was rotary evaporated off to leave a colorlessgel product (4.26 g, 65% yield, 98% purity) that was analyzed by ¹H NMRand LC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)C(O)OCH₂CH₂(CF₂)₆F. The product wasevaluated for CMC and surface tension beyond the CMC by Test Method 1;the results are shown in Table 2.

Comparative Example A

Maleic anhydride (0.63 g, 6.5 mmol),1H,1H,2H,2H-perfluoro-1-octanol(4.74 g, 13 mmol), p-toluenesulfonic acid monohydrate (p-TsOH) (0.19 g,1.0 mmol) and toluene (50 mL) were added to a flask and heated to refluxfor 96 hours at 111° C. The solution was separated and extracted withtwo washings of 5% sodium bicarbonate (50 mL each). The combined organicextracts were dried over anhydrous magnesium sulfate, and concentratedto remove the toluene at 140.30 mmHg (18.7 kPa) and 67° C.). Thestructure of the resulting liquid product di(1H,1H,2H,2H-perfluorooctyl)maleate (4.88 g, 93.4% yield, >80% purity) was confirmed by ¹H NMR andLC/MS.

Di(1H,1H,2H,2H-perfluorooctyl) maleate (4.70 g, 5.8 mmol, prepared asdescribed above) was added to isopropyl alcohol (isopropyl alcohol, 31g) and heated to 50° C. for a period of 10 min. with continual stirring.A solution of sodium bisulfite (0.61 g, 5.8 mmol) dissolved in deionizedwater (10 mL) was added dropwise to the solution. The mixture wasrefluxed for 22 h at 82° C. The progress was checked by LC/MS and afurther addition of aqueous sodium bisulfite (0.61 g, 5.9 mmol) wasadded. The mixture was refluxed for a further 70.3 h. The isopropylalcohol/water solution was removed by rotary evaporation to produce awhite solid. (2.70 g, 52.2% yield, 99% purity). The product compositionwas confirmed by ¹H NMR and LC/MS as the sodium salt ofdi(1H,1H,2H,2H-perfluorooctyl) maleate-2-sulfosuccinate. The product wasevaluated for CMC and surface tension beyond the CMC by Test Method 1;the results are shown in Table 1.

Comparative Example B

1H,1H,2H,2H-perfluorooctanol (8.02 g, 22 mmol), dicyclohexylcarbodiimide(DCC) (4.27 g, 21 mmol) and dichloromethane CH₂Cl₂, 35 mL) were added toa flask, equipped with a nitrogen inlet, overhead stirrer and twostoppers. The solution was cooled to 0° C. and the citraconic acid (1.28g, 9.8 mmol) dissolved in tetrahydrofuran (15 mL) was added dropwise.The solution was stirred for 10 min. and then the ice bath was removedto allow the solution to warm to room temperature. The mixture was leftto stir overnight. The resulting mixture was filtered to remove thetraces of 1,3-dicylcohexylurea that was produced as a by-product andthen washed with excess tetrahydrofuran (50 mL). The tetrahydrofuran andCH₂Cl₂ were concentrated at 378.14 mmHg (kPa) and 46° C.) and theproduct was dried in a vacuum oven for 3 hours. The product was analyzedthrough ¹H NMR and LC/MS, which indicated the conversion to monoester. Asimilar procedure was carried out again but with the addition of anothermole of alcohol. The alcohol (6.30 g, 13 mmol), DCC (2.63 g, 13 mmol)and CH₂Cl₂ (35 mL) were added to the flask and cooled to 0° C. Themonoester, that was produced previously, was re-dissolved intetrahydrofuran (15 mL) and added dropwise to the solution. The work-upmethod was carried out and the resulting product was a pale yellowliquid (6.46 g, 80.0% yield, 75% purity). The product was analyzed by ¹HNMR and LC/MS to confirm the structure as di(1H,1H,2H,2H-perfluorooctyl)citraconate.

Di(1H,1H,2H,2H-perfluorooctyl) citraconate (4.99 g, 6.1 mmol, preparedas described above) and isopropyl alcohol (32 g) were transferred to aflask and heated to 50° C. for 10 min. A solution of aqueous sodiumbisulfite (1.53 g, 15 mmol) dissolved in deionized water was added tothe solution and heated to reflux (82° C.) for 22 h. The white solid wasdried in an oven overnight (2.98 g, 53.0% yield, 95% purity). Theproduct composition was confirmed by ¹H NMR and LC/MS as the sodium saltof di(1H,1H,2H,2H-perfluorooctyl) citraconate-2-sulfosuccinate. Theproduct was evaluated for CMC and surface tension beyond the CMC by TestMethod 1, with results shown in Table 2, and spreading on cyclohexane byTest Method 2, with results shown in Table 3.

Comparative Example C

Maleic anhydride (17.2 g, 176 mmol), 1H,1H,2H,2H,-perfluorohexanol (93.1g, 353 mmol), p-toluenesulfonyl hydroxide (p-TsOH) (3.4 g, 17.6 mmol)and toluene (500 mL) were heated to reflux for 8 h. An additional amountof p-TsOH (3.4 g, 17.6 mmol) was added after 4 h of reflux. The solutionwas stirred overnight at room temperature. The solution was diluted withethyl acetate (500 mL) and washed three times with brine (250 mL each).The combined extracts were washed with a further washing of ethylacetate (300 mL). The combined organics were dried over anhydrous MgSO₄and concentrated to yield a colorless oil (85.8 g, 80% yield, 98%purity). The structure of the product was confirmed by ¹H NMR and LC/MSas di(1H,1H,2H,2H-perfluorohexyl) maleate.

Di(1H,1H,2H,2H-perfluorohexyl) maleate (1.5 g, 2.5 mmol, prepared asdescribed above) was added to isopropyl alcohol (32 g) and heated for aperiod of 10 min. until the two liquids became miscible. A solution ofsodium bisulfite (1.5 g, 14 mmol) dissolved in deionized water (15 mL)was transferred to the flask and the contents were heated to reflux at82° C. for 22 h. The white solid product resulted after the removal ofisopropyl alcohol/water solution (0.98 g, 55.8% yield, 99% purity). Theproduct composition was confirmed by ¹H NMR and LC/MS as the sodium saltof di(1H,1H,2H,2H-perfluorohexyl)) maleate-2-sulfosuccinate. The productwas evaluated for CMC and surface tension beyond the CMC by Test Method1, with results shown in Table 2, and spreading on cyclohexane by TestMethod 2, with results shown in Table 3.

Comparative Example D

Ethylene (25 g) was introduced to an autoclave charged with C₄F₉CH₂CF₂I(217 g) and d-(+)-limonene (1 g), and the reactor heated at 240° C. for12 hours. The product was isolated by vacuum distillation to provideC₄F₉CH₂CF₂CH₂CH₂I. Fuming sulfuric acid (70 mL) was added slowly to 50 gof C₄F₉CH₂CF₂CH₂CH₂I and mixture was stirred at 60° C. for 1.5 hours.The reaction was quenched with ice-cold 1.5 wt % Na₂SO₃ aqueous solutionand heated at 95° C. for 0.5 hours. The bottom layer was separated andwashed with 10 wt % aqueous sodium acetate and distilled to provideC₄F₉CH₂CF₂CH₂CH₂OH: bp 54-57° C. at 2 mmHg (267 Pa).

Trans-β-hydromuconic acid (0.94 g, 6.5 mmol), p-toluenesulfonic acidmonohydrate (0.12 g, 0.65 mmol), C₄F₉CH₂CF₂CH₂CH₂OH (4.29 g, 13 mmol)and toluene were added together and the contents were heated to refluxat 111° C. for 25 h. The work-up as in example 1 was conducted. Thewhite solid (3.82 g, 76.4% yield, 95% purity) analyzed by ¹H NMR andLC/MS to confirm the structure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH═CHCH₂C(O)OCH₂CH₂CF₂CH₂—C₄F₉.

The trans-β-hydromuconate, prepared as described above, (3.80 g, 5.0mmol) was added to isopropyl alcohol (31 g) and heated to 60° C. Asolution of aqueous sodium bisulfite (0.52 g, 5.0 mmol) was dissolved indeionized water and transferred to the mixture. The temperature wasraised to 82° C. and maintained for 22 h. The white precipitate wascollected by vacuum filtration and the filtrate was concentrated toremove the isopropyl alcohol/water solution. The white solid (3.88 g,89.9% yield, 98% purity was analyzed by ¹H NMR and LC/MS to confirm thestructure asC₄F₉CH₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)CH₂CH₂C(O)O—CH₂CH₂CF₂CH₂C₄F₉. Theproduct was evaluated for CMC and surface tension beyond the CMC by TestMethod 1; the results are shown in Table 2.

Comparative Example E

C₃F₇OCF₂CF₂I (100 g, 0.24 mol) and benzoyl peroxide (3 g) were chargedto a pressure vessel under nitrogen. A series of three vacuum/nitrogengas sequences was then executed at −50° C. and ethylene (18 g, 0.64 mol)was introduced. The vessel was heated for 24 hour at 110° C. Theautoclave was cooled to 0° C. and opened after degassing Then theproduct was collected in a bottle. The product was distilled giving 80 gof C₃F₇OCF₂CF₂CH₂CH₂I in 80% yield. The boiling point was 56˜60° C. at25 mm Hg (3.3 kPa).

A mixture of C₃F₇OCF₂CF₂CH₂CH₂I (300 g, 0.68 mol, prepared as describedabove) and N-methyl-formamide (300 mL), was heated to 150° C. for 26 h.Then the reaction was cooled to 100° C., followed by the addition ofwater to separate the crude ester. Ethyl alcohol (77 mL) and p-toluenesulfonic acid (2.59 g) were added to the crude ester, and the reactionwas stirred at 70° C. for 15 minutes. Then ethyl formate and ethylalcohol were distilled out to give a crude product. The crude productwas dissolved in ether, washed with aqueous sodium sulfite, water, andbrine in turn, then dried over magnesium sulfate. The product was thendistilled to give 199 g of C₃F₇OCF₂CF₂CH₂CH₂OH in 85% yield. The boilingpoint was 71-73° C. at 40 mm Hg (5.3 kPa).

Trans-β-hydromuconic acid (0.94 g, 6.5 mmol), C₃F₇OCF₂CF₂CH₂CH₂OH (4.30g, 13 mmol, prepared as described above), p-toluenesulfonic acidmonohydrate H (0.13 g, 0.65 mmol) and toluene (50 mL) were stirredcontinuously together and heated to reflux (111° C. for 25 h). Thework-up was carried out to produce a pale yellow liquid (3.90 g, 78.0%yield, 99% purity), which was analyzed by ¹H NMR and LC/MS to confirmthe structure asC₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH═CHCH₂C(O)O—CH₂CH₂CF₂CF₂OC₃F₇.

The trans-β-hydromuconate, prepared as described above, (3.88 g, 5.1mmol) was stirred continuously with isopropyl alcohol (31 g) for aperiod of 10 mins at an elevated temperature of 65° C. A solution ofsodium bisulfite (0.29 g, 2.8 mmol) dissolved in deionized water (14 mL)was added dropwise to the mixture. The temperature was raised to 82° C.and maintained for a period of 22 h. The solution was concentrated toremove the isopropyl alcohol, and the resulting liquid was left in avacuum oven overnight. The white solid (3.72 g, 84.4% yield, 87% purity)obtained was analyzed by ¹H NMR and LC/MS to confirm the structure asC₃F₇OCF₂CF₂CH₂CH₂OC(O)CH₂CH(SO₃Na)CH₂CH₂C(O)O—CH₂CH₂CF₂CF₂OC₃F₇. Theproduct was evaluated for CMC and surface tension beyond the CMC by TestMethod 1; the results are shown in Table 2.

TABLE 1 Comparative Examples and Surface Tension Measurements SurfaceTension Comparative CMC beyond CMC Example R_(f) X (wt %) (mN/m) Comp.Ex. A C₆F₁₃ —CH₂—CH—(SO₃M)— 0.024 13.8 Comp. Ex. B C₆F₁₃—CH₂—CH(CH₂—SO₃M)— 0.068 16.3 Comp. Ex. C C₄F₉ —CH₂CH—(SO₃M)— 0.26 17.1Comp. Ex. D C₄F₉CH₂CF₂CH₂—CH₂— —CH₂CH(SO₃M)—CH₂CH₂— 0.33 18.0 Comp. Ex.E C₃F₇OCF₂CF₂CH₂—CH₂— —CH₂CH(SO₃M)—CH₂CH₂— 0.88 20.8

TABLE 2 Formulae 1A, 1B, and 1C and Surface Tension MeasurementsCritical Surface Micelle Tension Concn. Beyond CMC Ex. R_(a) X (wt %)(mN/m) 16 C₃F₇OCF(CF₃)CONH—CH₂CH₂— —CH₂CH(SO₃M)— 0.016 22.0 17C₄F₉CH₂CF₂CH₂CH₂— —CH₂CH(SO₃M)— 0.051 18.9 18 C₄F₉CH₂CF₂CH₂CF₂—CH₂CH₂——CH₂CH(SO₃M)— 0.014 20.7 19 C₃F₇OCF₂CF₂CH₂CH₂— —CH₂CH(SO₃M)— 0.034 17.120 C₃F₇OCFHCF₂O—CH₂CH₂OCH₂CH₂— —CH₂CH(SO₃M)— 0.039 17.8 21C₂H₅CH₂CH₂[(CF₂CF₂)_(i)—(CH₂CH₂)_(j)]_(k) —CH₂CH(SO₃M)— 0.028 21.1 22C₃F₇OCF(CF₃)CONH—CH₂CH₂— —CH₂CH(CH₂SO₃M)— 0.083 18.2 23C₄F₉CH₂CF₂CH₂CH₂— —CH₂CH(CH₂SO₃M)— 0.0095 19.4 24C₃F₇OCF(CF₃)CONH—CH₂CH₂— —CH(CH₃)CH(SO₃M)— 0.095 25.6 25C₄F₉CH₂CF₂CH₂CH₂— —CH(CH₃)CH(SO₃M)— 0.019 16.8 26 C₄F₉CH₂CF₂CH₂CH₂——CH₂CH(SO₃M)CH₂— 0.042 18.0 27 C₄F₉CH₂CF₂CH₂CF₂—CH₂CH₂— —CH₂CH(SO₃M)CH₂—0.030 18.2 R_(a)/R  28* C₄F₉CH₂CF₂CH₂CH2—/ —CH₂CH(SO₃M)— 0.064 19.7 —H29 C₄F₉CH₂CF₂CH₂CH₂—/ —CH₂CH(SO₃M)— 0.038 16.0 —(CH₂)₆H R_(a)/R_(f) 30C₄F₉CH₂CF₂CH₂CH₂—/ —CH₂CH(SO₃M)— 0.023 20.8 —(CF₂)₆F *Example 28 wasmeasured at pH 3.0. Since the R_(a) is H, the performance of thecompound is sensitive to pH.

Table 2 shows that the surfactants of the invention gave low criticalmicelle concentrations (less than 0.1 weight percent) and low surfacetension levels beyond CMC (less than 20 mN/m in water). Table 1 providesdata for Comparative Examples. Comparative Example C, having an R_(f) ofC₄F₉ contained a similar fluorine level to the Examples of theinvention, but had a far higher CMC value, thus indicating superiorperformance by the Examples of the invention. Comparative Examples A andB each contained an R_(f) of C₆F₁₃, which was a higher fluorine levelthan the Examples of the invention. The Examples of the invention hadCMC values similar to Comparative Examples A and B despite the lowerlevel of fluorine. Thus the Examples of the invention had a higher levelof fluorine efficiency in providing comparable performance with lessfluorine present. Beyond the CMC all of the examples demonstratedcomparable surface tension.

TABLE 3 Spreading on Cyclohexane Spreading Hydrocarbon surfactant oncyclohexane Performance Ex. # Trials (I) and (II) (extent and time)Category 17 I) SIMULSOL SL8 30% in 30 s Good II) TRITON X100 Floatswithout spreading Fair 18 I) SIMULSOL SL8 50% in 30 s Good II) TRITONX100 100% in 30 seconds Excellent 19 I) SIMULSOL SL8 Sink immediatelyPoor II) TRITON X100 70% in 40 s Good 20 I) SIMULSOL SL8 100% in 6seconds Excellent II) TRITON X100 50% in 30 s Good 22 I) SIMULSOL SL850% in 10 s Good II) TRITON X100 Floats without spreading Fair 23 I)SIMULSOL SL8 20% in 20 s Good II) TRITON X100 100% in 25 s Excellent 25I) SIMULSOL SL8 10% in 20 s Good II) TRITON X100 Sink immediately Poor29 I) SIMULSOL SL8 100% in 3 s Excellent II) TRITON X100 100% in 3 sExcellent B I) SIMULSOL SL8 Sink immediately Poor II) TRITON X100 Sinkimmediately Poor C I) SIMULSOL SL8 Sink immediately Poor II) TRITON X100Sink immediately Poor

Table 3 shows that the surfactants of the present invention, whencombined with hydrocarbon surfactant SIMULSOL SL8 or TRITON X100 in anaqueous formulation, spread more quickly and more completely acrosscyclohexane than either Comparative Example B or C, which both sank.Spreading across cyclohexane is predictive of an effective fire fightingfoam. Table 3 shows that low critical micelle concentrations and lowSurface Tension levels beyond CMC are necessary but not sufficientcriteria for an effective fire fighting foam.

1. A compound of Formula 1A, 1B, or 1C(R_(a)—O—CO—)₂X  Formula 1AR_(a)—O—CO—X—CO—O—(CH₂CH₂)R_(f)  Formula 1BR_(a)—O—CO—X—CO—O—R  Formula 1C wherein R_(a) is the group (i)R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—; (ii) R_(f)OCF₂CF₂—(C_(g)H_(2g))—;(iii) R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—; (iv)R_(f)OCFHCF₂O(C_(w)H_(2w)); (v) R_(f)OCF(CF₃)CONH—(C_(g)H_(2g))—; or(vi) R_(f)(CH₂)_(h)[(CF₂CF₂)_(i)(CH₂CH₂)_(j)]_(k) each R_(f) isindependently C_(c)F_((2c+1)); c is 2 to about 6; d is 1 to about 3; gis 1 to 4; v is 1 to about 4; w is from about 3 to about 12; h is 1 toabout 6; i, j, and k are each independently 1, 2, or 3, or a mixturethereof; provided that the total number of carbon atoms in group (vi) isfrom about 8 to about 22; X is a linear or branched difunctional alkylsulfonate group—C_(e)H_((2e−1))(SO₃M)-, wherein e is 2 or 3; M is a monovalent cationselected from the group consisting of hydrogen, ammonium, alkali metal,and alkaline earth metal; R is H or a linear or branched alkyl groupC_(b)H_((2b+1))—; and b is from 1 to about
 18. 2. The compound of claim1 wherein R_(a) is R_(f)(CH₂CF₂)_(d)—(C_(g)H_(2g))—;R_(f)OCF₂CF₂—(C_(g)H_(2g))—; R_(f)OCFHCF₂O(CH₂CH₂O)_(v)—(C_(g)H_(2g))—;or R_(f)OCFHCF₂O(C_(w)H_(2w))—.
 3. The compound of claim 1 wherein c is3 or
 4. 4. The compound of claim 1 wherein X is CH₂CH(SO₃M),CH₂CH(CH₂SO₃M), CH(CH₃)CH(SO₃M), CH₂CH(SO₃M)CH₂, or CH₂CH(SO₃M)CH₂CH₂.5. The compound of claim 2 wherein d is 1, g is 2, and R_(f) is C₃F₇ orC₄F₉.
 6. The compound of claim 5 wherein X is C₃H₅(SO₃Na) orCH₂CH(SO₃Na).
 7. The compound of claim 1 wherein R_(a) isC₄F₉CH₂CF₂CH₂CH₂ or C₃F₇CH₂CF₂CH₂CH₂ and R_(f) is (CF₂)₆F.
 8. A methodof altering the surface behavior of a liquid comprising adding to theliquid a compound of claim 1 or a mixture thereof.
 9. The method ofclaim 8 wherein the altering of surface behavior is lowering the surfacetension.
 10. The method of claim 8 wherein the surface behavior isselected from the group consisting of wetting, penetration, spreading,leveling, flowing, emulsifying, dispersing, repelling, releasing,lubricating, etching, bonding, and stabilizing.
 11. The method of claim8 wherein the liquid is a coating composition, latex, polymer, floorfinish, ink, emulsifying agent, foaming agent, release agent, repellencyagent, flow modifier, film evaporation inhibitor, wetting agent,penetrating agent, cleaner, grinding agent, electroplating agent,corrosion inhibitor, etchant solution, soldering agent, dispersion aid,microbial agent, pulping aid, rinsing aid, polishing agent, personalcare composition, drying agent, antistatic agent, floor finish, orbonding agent.